Although silicon (Si) nanostructures exhibit size dependent light emission, which can be attributed to quantum confinement, the role of surface passivation is not yet fully understood. This understanding is central to the development of nanocrystal-based detectors. This study investigated the growth, surface chemistry, passivation with deuterium (D2), ammonia (ND3) and diborane (B2D6) and the resulting optical properties of Si nanostructures. Si nanocrystals less than 6 nm in diameter are grown on SiO2 surfaces in an ultra high vacuum chamber using hot-wire chemical vapor deposition and the as grown surfaces are exposed to atomic deuterium. Temperature programmed desorption (TPD) spectra show that that the nanocrystals surfaces are covered by a mix of monodeuteride, dideuteride and trideuteride species. The manner of filling of the deuteride states on nanocrystals differs from that for extended surfaces as the formation of the dideuteride and trideuteride species is facilitated by the curvature of the nanocrystal. No photoluminescence (PL) is observed from the as grown unpassivated nanocrystals. As the deuterium dose is increased, the PL intensity also begins to increase. This can be associated with increasing amounts of mono-, di- and trideuteride species on the nanocrystal surface, which results in better passivation of the dangling bonds and relaxing of the reconstructed surface. At high deuterium doses, the surface structure breaks down and amorphization of the top layer of the nanocrystal takes place. Amorphization reduces the PL intensity. Finally, as the nanocrystal size is varied, the PL peak shifts, which is characteristic of quantum confinement. The dangling bonds and the reconstructed bonds at the NC surface are also passivated and transformed with D and NDx by using deuterated ammonia (ND3), which is predissociated over a hot tungsten filament prior to adsorption. At low hot wire ND3 doses PL emission is observed at 1000 nm corresponding to reconstructed surface bonds capped by predominantly monodeuteride and Si-ND2 species. As the hot wire ND3 dose is increased, di- and trideuteride species form and intense PL is observed around 800 nm that does not shift with NC size and is associated with defect levels resulting from NDx insertion into the strained Si-Si bonds forming Si2=ND. The PL intensity at 800 nm increases as the ND3 dose is increased and the intensity increase is correlated to increasing concentrations of deuterides. At extremely high ND3 doses PL intensity decreases due to amorphization of the NC surface. In separate experiments, Si NCs were subjected to dissociative (thermal) exposures of ammonia followed by exposures to atomic deuterium. These NCs exhibited size dependent PL and this can be attributed to the prevention of the formation of Si2=ND species. Finally, deuterium-passivated Si NCs are exposed to BDx radicals formed by dissociating deuterated diborane (B2D6) over a hot tungsten filament and photoluminescence quenching is observed. Temperature programmed desorption spectra reveal the presence of low temperature peaks, which can be attributed to deuterium desorption from surface Si atoms bonded to subsurface boron atoms. The subsurface boron likely enhances nonradiative Auger recombination. / text

published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

The chromogenic properties of tungsten trioxide (WO3) have been studied by photoluminescence spectroscopy at 4.2 K in order to characterize the electronic structure of this material and see how this relates to optical responses during chromogenic coloration. Transition processes between electron energy states are often the cause of optical phenomena and it is important to identify such processes in order to understand the chromogenic coloration of tungsten oxide films. Much research work has been devoted to characterize the physical and chemical mechanisms that are responsible for this coloration and this is of fundamental importance to understand the chromogenic behavior. The latest research shows that oxygen vacancies could play an important role in certain coloration processes, but it is still a matter of debate whether these are important for the overall response. This work aims to identify specific transitions that are related to oxygen vacancies by measuring photoluminescence from films with controlled vacancy content. The main goal of the project was to set up an experiment that could measure photoluminescence at liquid helium temperature. This was done by installing and integrating the components included in this experimental set-up. The films had been prepared prior to this work and were deposited on a nanocrystalline CaF2 substrate, which is a material that has a very large band gap and was therefore expected to fully transparent in the UV range. However it was found that the substrate inelastically scattered the UV excitation light, which produced strong signals that overshadowed the photoluminescence and prevented an effective characterization of the electronic structure in the films. Instead, suggestions were given on how to minimize uncertainty factors and overcome the difficulties met in this work. It was also found that the films attain a lasting blue coloration by exposure to UV light in vacuum, and that this might be due to oxygen being desorbed from the film during experiments in vacuum.

Microbeam radiation therapy (MRT) is a potential cancer therapy technique that uses an intense X-ray beam produced by a synchrotron. In MRT, an array of microplanar beams, called a microbeam, is delivered to a tumour. The dose at each centre of planar beams is extremely large (several hundred grays) while dose level in the valley between the peaks is below several tens of gray. Moreover, the width of each planar beam is typically 20 - 50 µm, and the distance from a centre of planar-beam to that of adjacent beam is 200 - 400 µm. For the latter reasons, the fundamental requirements for the dosimetry technique in MRT are (1) a micrometer-scale spatial resolution and (2) detection sensitivity at large doses (5 - 1000 Gy). No existing detectors can satisfy those two requirements together. The objective of the Ph.D. research is to develop a prototype dosimetry technique which fulfils the requirements for measuring the dose profile in the microbeam. The currently used approach relies on the indirect detection of X-rays; in which the X-ray dose is recorded on a detector plate, and then the recorded signals are digitized using a reader. Our proposed approach utilizes Sm3+-doped polycrystallites, glasses, and/or suitable glass-ceramics (though our approach is not limited to the use of Sm ion) for the detector plate, in which a valence reduction of Sm3+, that is the conversion of Sm3+ to Sm2+, takes place upon irradiation of X-rays. The extent of reduction is further read out using confocal fluorescence microscopy via the photoluminescence (PL) signals of Sm3+ and Sm2+. The work carried out throughout the course of the research includes the construction of confocal fluorescence microscopy, synthesis and characterizations of dosimeter materials, as well as application tests of our approach for measuring the dose profile of a microbeam used at synchrotron facilities -- Canadian Light Source (CLS), Saskatoon, Canada, European Synchrotron Radiation Facility (ESRF), Grenoble, France, and SPring-8, Hyogo, Japan. Further, the research has shown that 1 % Sm-doped fluoroaluminate glass is one of the best candidates for the type of dosimetric application. It has the dynamic range of ~1 to over 1000 Gy which covers the dose range used in MRT, excellent signal-to-noise ratio (large extent of Sm3+ → Sm2+ change), and excellent stability of recorded signal over time. The recorded signal in the detector is erasable by heating or exposing to light such as UV. Furthermore, with a use of confocal microscope, it has ability to measure the distribution pattern of dose over the cross-section of microbeam. Therefore, we believe that our approach is one of the most promising techniques available.

A close relation between structural and optical properties of any semiconductor material does exist. An adequate knowledge and understanding of this relationship is necessary for fabrication of devices with desired optical properties. The structural quality and hence the optical properties can be influenced by the growth method and the substrate used. The aim of this work was to investigate the change in optical properties caused by growth techniques and substrate modification. To study the influence of growth technique on optical properties, ZnO nanostructures were grown using atmospheric pressure metal organic chemical vapor deposition (APMOCVD) and chemical bath deposition (CBD) technique. The structural and optical investigations were performed using scanning electron microscopy (SEM) and micro photoluminescence (μ-PL), respectively. The results revealed that the grown structures were in the shape of nano-rods with slightly different shapes. Optical investigation revealed that low temperature PL spectrum for both the samples was dominated by neutral donor bound excitons emission and it tends to be replaced by free exciton (FX) emission in the temperature range of 60-140K. Both excitonic emissions show a typical red-shift with increase in temperature but with a different temperature dynamics for both the sample and this is due to difference in exciton-phonon interaction because of the different sizes of nano-rods. Defect level emission (DLE) is negligible in both the sample at low temperature but it increased linearly in intensity after 130 K up to the room temperature.Modification in substrate can also play a significant role on structural and optical properties of the material. Specially variation in the miscut angle of substrate can help to control the lateral sizes of the Nanostructures and thus can help to obtain better structural andoptical quality. Also optical quality is a key requirement for making blue and ultraviolet LEDs. Therefore, ZnO Nanostructures were grown on SiC on-axis and off-axis substrates having different off-cut angles. Morphological investigation revealed thatgrown structures are epitaxial for the case when substrate off-cut angle is higher and deposition rate is low. Low temperature PL spectrum of all the samples was dominated by neutral donor bound excitons and free exciton emission become dominant at 100 K for all the samples which completely eliminate the neutral donor bound excitonic emission at 160K. Two electron satellite of the neutral donor bound excitons and LO phonons of excitonic features are also present. A typical red-shift in excitonic features was evident in temperature dependence measurement. Red-shift behavior of free exciton for all the samples was treated by applying Varshni empirical expression and several important parameter, such as, the Debye temperature and the band gap energy value was extracted. Thermal quenching behavior was also observed and treated by thermal quenching expression and value of the activation energy for non-radiative channel was extracted. The results that are obtained demonstrate a significant contribution in the fields of ZnO based nano-optoelectronics and nano-electronics.

Magic-sized nanocrystals (MSNs) are nanocrystals with a single size distribution. They have narrow spectral features that do not exhibit inhomogeneous line broadening. This enabled us to analyze homogeneous line broadening of CdSe and CdTe MSNs. In solution, we observed two aggregated configurations of CdSe and CdTe MSNs. Sub-peaks within MSN excitonic peaks were caused by these two aggregated configurations and surface states. A two-dimensional photoluminescence spectrum of a mixture of CdTe 427 nm and 500 nm MSNs gave direct evidence of Förster resonant energy transfer (RET) between the two sizes of MSNs. Normalized experimental overlap between donor emission and acceptor absorption spectra was on the order predicted by theory, confirming that there is sufficient overlap for RET to take place in this system. Additionally, within both aggregated configurations, the two sizes of MSNs were within sufficient distance from one another for RET to occur.

Magic-sized nanocrystals (MSNs) are nanocrystals with a single size distribution. They have narrow spectral features that do not exhibit inhomogeneous line broadening. This enabled us to analyze homogeneous line broadening of CdSe and CdTe MSNs. In solution, we observed two aggregated configurations of CdSe and CdTe MSNs. Sub-peaks within MSN excitonic peaks were caused by these two aggregated configurations and surface states. A two-dimensional photoluminescence spectrum of a mixture of CdTe 427 nm and 500 nm MSNs gave direct evidence of Förster resonant energy transfer (RET) between the two sizes of MSNs. Normalized experimental overlap between donor emission and acceptor absorption spectra was on the order predicted by theory, confirming that there is sufficient overlap for RET to take place in this system. Additionally, within both aggregated configurations, the two sizes of MSNs were within sufficient distance from one another for RET to occur.

Controlling the quantum states of charge (excitons) or spin-polarized carriers in semiconductor quantum dots (QDs) has been the focus of a considerable research effort in recent years due to the strong promise of using this approach to develop solid state quantum computing hardware. The long-term scalability of this type of quantum computing architecture is enhanced by the use of QDs emitting in the telecom band, which would exploit the established photonic infrastructure. This thesis reports the use of all optical infrared experimental techniques to control exciton dynamics in two different QD samples consisting of InAs/GaAs QDs and InAs/InP QDs within a planar microcavity. An infrared quantum control apparatus was developed and used to apply optimized shaping masks to ultrafast pulses from an optical parametric oscillator. Pulse shaping protocols designed to execute a two-qubit controlled-rotation operation on an individual semiconductor QD were demonstrated and characterized. The quantum control apparatus was then implemented in simultaneous single qubit rotations using two uncoupled, distant InAs/GaAs QDs. These optimal control experiments demonstrated high fidelity optical manipulation of exciton states in the two QDs using a single broadband laser pulse, representing a step forward on the path to a scalable QD architecture and showcasing the power of pulse shaping techniques for quantum control on solid state qubits. As an alternative to single QDs, which have very low optical signals, subsets of QDs within an ensemble can be used in quantum computing applications. To investigate the mediation of inhomogeneities in a QD ensemble, pump-probe experiments were performed on InAs/InP QDs within a dielectric Bragg stack microcavity. Two different excitation geometries showed that the angle dependence of the microcavity transmission allowed for the spectral selection of QD subsets with transition energies resonant with the cavity mode. The microcavity mitigated inhomogeneities in the ensemble while providing a basis for addressing QD subsets which could be used as distinguishable quantum bits. This thesis work shows significant advances towards an optical computing architecture using quantum states in semiconductor QDs.

Disertacija skirta krūvininkų rekombinacijos tyrimams plačiatarpiuose nitridiniuose puslaidininkiuose bei jų dariniuose. Kompleksiniai eksperimentiniai tyrimai buvo atlikti naudojant kelias skirtingas metodikas. Atlikti krūvininkų dinamikos GaN sluoksniuose tyrimai labai žemų ir aukštų sužadinimų sąlygomis. Pasiūlytas naujas liuminescencijos gesimo kinetikų interpretavimo metodas, siejant liuminescencijos ir šviesa indukuotų dinaminių gardelių kinetikas. Naujas požiūris į geltonosios liuminescencijos juostą GaN sluoksniuose leido susieti geltonosios liuminescencijos intensyvumą su krūvininkų gyvavimo trukme. Skirtingomis technologijomis augintų AlGaN sluoksnių palyginimas suteikė informacijos apie juostos potencialo fliuktuacijas bei krūvininkų gyvavimo trukmę ribojančius veiksnius AlGaN medžiagose. Atskleista naujų krūvininkų dinamikos daugialakštėse AlGaN/AlGaN kvantinėse duobėse ypatumų – vidinio elektrinio lauko bei kvantinės duobės pločio fliuktuacijų sąlygotos lokalizacijos įtaka krūvininkų dinamikai. Dauguma tirtų bandinių buvo auginti naudojant MEMOCVDTM technologiją ir tyrimai patvirtino šios technologijos potencialą siekiant pagerinti medžiagų kokybę. / The thesis is dedicated to carrier recombination investigations in wide-band-gap semiconductors and their structures. The complex experimental studies were performed by combining several different techniques. Carrier dynamics in GaN epilayers were investigated under extremely low and high excitation conditions. A new method for interpreting photoluminescence decay kinetics was suggested by interrelating luminescence and light-induced grating decay transients. The new approach for studies of yellow band in GaN was shown by linking the carrier lifetime with yellow band intensity. Two AlGaN epilayers grown by different novel growth techniques were compared and the factors limiting carrier lifetime were identified. Moreover, more evidence on alloy mixing and band potential fluctuations in AlGaN was provided by our study. Essential knowledge was attained about carrier dynamics in high-Al-content AlGaN/AlGaN multiple quantum well structures: the influence of built-in electric field and carrier localization on carrier dynamics. Most of the samples under study were grown by MEMOCVDTM growth technique, and our study confirmed the high potential of this innovative growth technique for improving material quality.

The thesis is dedicated to carrier recombination investigations in wide-band-gap semiconductors and their structures. The complex experimental studies were performed by combining several different techniques. Carrier dynamics in GaN epilayers were investigated under extremely low and high excitation conditions. A new method for interpreting photoluminescence decay kinetics was suggested by interrelating luminescence and light-induced grating decay transients. The new approach for studies of yellow band in GaN was shown by linking the carrier lifetime with yellow band intensity. Two AlGaN epilayers grown by different novel growth techniques were compared and the factors limiting carrier lifetime were identified. Moreover, more evidence on alloy mixing and band potential fluctuations in AlGaN was provided by our study. Essential knowledge was attained about carrier dynamics in high-Al-content AlGaN/AlGaN multiple quantum well structures: the influence of built-in electric field and carrier localization on carrier dynamics. Most of the samples under study were grown by MEMOCVDTM growth technique, and our study confirmed the high potential of this innovative growth technique for improving material quality. / Disertacija skirta krūvininkų rekombinacijos tyrimams plačiatarpiuose nitridiniuose puslaidininkiuose bei jų dariniuose. Kompleksiniai eksperimentiniai tyrimai buvo atlikti naudojant kelias skirtingas metodikas. Atlikti krūvininkų dinamikos GaN sluoksniuose tyrimai labai žemų ir aukštų sužadinimų sąlygomis. Pasiūlytas naujas liuminescencijos gesimo kinetikų interpretavimo metodas, siejant liuminescencijos ir šviesa indukuotų dinaminių gardelių kinetikas. Naujas požiūris į geltonosios liuminescencijos juostą GaN sluoksniuose leido susieti geltonosios liuminescencijos intensyvumą su krūvininkų gyvavimo trukme. Skirtingomis technologijomis augintų AlGaN sluoksnių palyginimas suteikė informacijos apie juostos potencialo fliuktuacijas bei krūvininkų gyvavimo trukmę ribojančius veiksnius AlGaN medžiagose. Atskleista naujų krūvininkų dinamikos daugialakštėse AlGaN/AlGaN kvantinėse duobėse ypatumų – vidinio elektrinio lauko bei kvantinės duobės pločio fliuktuacijų sąlygotos lokalizacijos įtaka krūvininkų dinamikai. Dauguma tirtų bandinių buvo auginti naudojant MEMOCVDTM technologiją ir tyrimai patvirtino šios technologijos potencialą siekiant pagerinti medžiagų kokybę.